One-dimensional steady transport by molecular dynamics simulation: Non-Boltzmann position distribution and non-Arrhenius dynamical behavior

TL;DR

This study uses molecular dynamics to analyze particle transport in a 1D system, revealing non-Boltzmann position distributions and non-Arrhenius temperature dependence of mobility and diffusion, challenging classical assumptions.

Contribution

It introduces an accurate method to measure drift velocity under weak forces and uncovers deviations from classical laws in a non-equilibrium steady state.

Findings

Mobility and diffusion obey Einstein relation.

Temperature dependence deviates from Arrhenius law.

Position distribution deviates from Boltzmann distribution.

Abstract

A non-equilibrium steady state can be characterized by a nonzero but stationary flux driven by a static external force. Under a weak external force, the drift velocity is difficult to detect because the drift motion is feeble and submerged in the intense thermal diffusion. In this article, we employ an accurate method in molecular dynamics simulation to determine the drift velocity of a particle driven by a weak external force in a one-dimensional periodic potential. With the calculated drift velocity, we found that the mobility and diffusion of the particle obey the Einstein relation, whereas their temperature dependences deviate from the Arrhenius law. A microscopic hopping mechanism was proposed to explain the non-Arrhenius behavior. Moreover, the position distribution of the particle in the potential well was found to deviate from the Boltzmann equation in a non-equilibrium steady state. The non-Boltzmann behavior may be attributed to the thermostat which introduces and effective "viscous" drag opposite to the drift direction of the particle.